N-(decachloro-3-hydroxypentacyclo (5, 3, 0, 02, 6. 04, 10. 05, 9) decyl-3) amides and carbamate esters



United States Patent N (DECACHLORO, .3 IIYDROXYPENTACYCLO (5,3 0,0 -0%-0 )DECYL-3) AMIDES AND CAR- BAMATE' ESTERS i t Y Edward D. Weil,Lewiston, and Keith J.. Smith, Lockport, N.Y., assignors to HookerChemical Corpogitiogn, Niagara Falls, N.Y., a corporation or New or Y N0Drawing. Filed Nov. 30, 1965, Ser. No; 510,680

I Claims. (Cl. 260-326) r This is a 'co'ntinuationdn-part of mycopending application Ser. No. 97,771, filed March 23, 1961, now US.Patent 3,281,453. I I 1 v This invention concerns novel pentacycliccompositions of matter useful as toxicants and intermediates for organicsynthesis. More particularly, this invention describes a new class ofcompounds, N-(decachloro-3-hydroxypentacyclo(5.3.0.0 .0 .0 decyl-3)amides, which because of their apparent toxicity or repulsion towardlower forms ,of marine life such as barnacles, function effectively asmarine fouling retardants. The. scope of the present inventionencompasses the compounds Withirithe generic formula below (numbering ofthe positions is shown) of hydrogen, alkyl, substituted alkyl, aryl,substituted aryl, R is a member selected from the group consisting ofhydrogen, alkyl, substituted alkyl, aryl, substituted aryl, amino,substituted amino, alkoxy, and aryloxy, X is an element selected fromthe group consisting of sulfur and oxygen, oxygen being preferred forreasons of cost and, generally, stability. i

The group R or R may be of high molecular weight and either or both mayin fact represent macromolecular chains; and the compositions of theinvention may, therefore, be macromolecular (polymeric) substances aswel as lower molecular weight substances.

For the sake of simplicity the below portion of the generic formulagiven previously will be referred to as 10 10( 3,345,378 Patented Oct.3, 1967 CmClMOHi-NHC ONH,

CO-GH cmchowm-n C O 0 H2 011,011, mammoth-N cH,

' coorncn,

and related structures.

In the latter five structures at represents the degree ofpolymerization, greater than one and with no upper limit. Thesemacromolecular products of the invention may be made by the same generalprocess as the lower molecular weight products, and are characterized bythe same type of anti-fouling activity, while at the same time retainingcertain of the desirable physical properties of the parentmacromolecular compound, such as the ability to form films. Beingresins, these products may serve not only as anti-fouling components'of'marine paints but also as filmforming or film-reinforcingingredients.

The foregoing list oflcompounds is merely intended to be illustrative ofthe scope of this invention and is not in any sense intended to limit ordefine the invention.

While the causes of marine fouling are presently obscure, its effect oneconomic and military affairs is readily apparent. It is estimated thatthe cost of preventing, slowing down and treating marine fouling runsinto millions of dollars annually, and no satisfactory solution is insight. For example, the efficiency and the period of use of a pier,ship, boat, buoy or marine structure is greatly reduced unless someprophylactic treatment is followed. Ships which have become encrustedwith marine organisms lose a substantial part of their normal speed andmechanical efliciency. Furthermore, many ships and marine structuressuch as bulkheads, buoys, off-shore radar towers and oil drilling rigsand platforms once fouled are much more prone to become corroded orrotted. For this reason, an extensive and costly program of prophylaxisand maintenance is followed in an effort to cut down the even moreexpensive deleterious effects of the marine fouling.

The most common method of reducing the amount of the shell-likeencrustation built up by the lower forms of marine life such asbarnacles or other lower marine creatures is to paint the material to beprotected with a special copper oxide based paint. However, the amountof copper oxide required adversely effects the physical characteristicsof the paint and its normal life is reduced. In addition, the presenceof a large quantity of copper oxide on a metal boat or ship willeventually create an electrolytic cell which greatly accelerates thetendency toward corrosion. To prevent this electrolytic corrosion thesurface must first be covered by an additional and expensive coat ofpaint to insulate the copper oxide from the hull. But even when soprotected, the hull of any ship or boat must be routinely scraped toremove the fouled surface which forms though albeit more slowly.Obviously too, this is expensive, since in addition to requiring costlyand time-consuming dry-docking, scraping and repainting, the ship isremoved from profitable use. For the above reasons, it can readily beseen that the discovery of compounds possessing anti-marine foulingproperties at low concentrations is of extreme commercial and navalimportance. While the mechanism by which the compounds of this inventionretard marine fouling is not understood, it has been found that thesecompounds function well at economically feasible concentrations, arenon-corrosive in themselves and being readily compatible with the oils,bases and adjuvants commonly used in points can readily be formulated inmarine paints and coatings in general.

While the compounds of this invention are advantageous as anti-marinefouling agents, they possess in addition other important advantages. Forexample, the novel compositions of this invention are useful as fireretardants and mildew retardants when formulated in organic coatlIlgS.

In addition, these compositions may be used as intermediates in thepreparation of other anti-fouling compositions. Thus, when is produced.This compound also has activity as a marine anti-fouling substance.

A related but ancillary advantage that the compounds of this inventionpossess generally is that they are valuable intermediates for organicsynthesis, in that the reactive and free OH group may be furtherreplaced by NRC(=X)R where R, R and X have the same meaning aspreviously defined.

A further attribute that these compounds possess as syntheticintermediates is that in many instances they form complex additioncompounds with water, amines, and even with additional moles of amidebeyond the stoichiometrically combined amount. This characteristic isbelieved to be due to the ability of the OH group to form a hydrogenbond with an electron-rich atom, particularly with a divalent oxygenatom or a trivalent nitrogen atom. For example, the product C Cl (OH)NHCHO when dissolved in an excess of formamide, and the solution thenpoured into water, forms a more or less hydrated solid complexapproximating to A further characteristic of the .new compounds of theinvention is that they have weak acidic properties, per.- haps due tothe --OH group butalso in some cases perhaps due to the NHCO- group.Regardless of the theoretical reasons, it has empirically been foundthat strong bases such as sodium methoxide, hydroxide, and the like canform salts with the compounds of the invention. Since the abovementioned salts and complexes can revert to the parent compounds of theinvention, they constitute usable formulations for the purposes ofantifouling coatings, a fact which we have impiri-cally con- The novelcompoupnds of thisinvention may be prepared by reactinghexachlorocyclopentadiene with chlorosulfonic acid, then heating theintermediate that forms in an appropriate solvent with atleast one molarequivalent of an amide or trioamide of the structure NHRC(=X)R'. Theamide NHR(C=X)R' may be added at the beginning of the heating,graduallyduring the heating, or after the heating has commenced forseveral hours. The rate and order of addition has not been foundv to bea critical feature of our process. It has also been found possible toemploy polymeric compounds having a free and reactive structureNHRC(=X)R' as reactants, for example, proteins, nylon, partially orfully hydrolyzed acrylonitrile polymers or coploymers and thepolyurethanes. Starting with macromolecular amides, macromolecularproducts are obtained. -Itis not necessary to use a solvent for thereaction when the amide NHRC(=X)R' is a. liquid or low melting solid,but where the amide is,not easily fused, a solvent is convenient.Appropriate solvents include but are not limited to chlorinatedhydrocarbons, such as chlorobenzene or acetylene tetra chloride,aliphatic and aromatic compounds such asv cyclohexane, xylene ortoluene; ketones such as methyl ethyl and methyl propyl ketone, etherssuch as diethyl, dipropyl, isobutyl, nitrohydrocar-bons such as thenitrobenzen'es, esters such as the lower alkyl acetates, N,N-diallsylamides such as dimethylformamide and acids such as formic acid. Wherethe NHRC(=X)R' is a liquid the solvent may be dispensed with using anexcessof the amide or thioamide instead. The temperatures needed toinitiate and continue this reaction are not critical and varyconsiderably according to the reactants used. However, the extremes havebeen found to be from about zero degrees centigrade to two hundreddegrees centrigrade with a satisfactory range generally being betweentwenty degrees and one hundred and seventy-five degrees centrigrade.Similarly, the time for the reaction to become compelte, as measured byinfra-red analysis, varies according to several factors such astemperature and reactants. Many reactions are completed in less than anhour, but others ocasionally take as long as a day. The reaction mayalso be followed by checking the rate of S which is evolved, thereaction being halted when theflow of S0 has substantially ceased. Avariation of the above process'is to use a nitrile or imide capable ofbeing hydrolyzed to the desired amide NHR(( =X)R plus at least thestoichiometric quantity of water required for said hydrolysis, thehydrolysis being run concurrently with the reaction of the invention.The structures of the products are proved by elemental analysis byinfra-red spectra which shows the OH group absorption and thecharacteristic amide C=O or thioamide C=Sbands1 The presence of thepentacyclo (5.3.00 .0 .0 decane skeleton is proved byfu'si'o'n withseveral parts byw'eight of PCl in a sealed tube at elevatedtemperatures, which yields the known dodecachloropentacyclo-(5.3.0.0 .0.0 decane, melting point four hundred and eighty-five degrees. Amoredetailed discussion of the process and compositions produced ispresented in the examples which follow. 4

Example 1.Preparati0n of C Cl (OH) (NHCOCH Hexachlorocyclopentadiene isreacted with chlorosulfonic acid as disclosed in US. Patent 2,516,404,an intermediate (described in said patent asC 'H O SCl isformed whichhas a melting point. of'oue hundred, and forty-six to one hundred andforty-eight degrees centigrade. This intermediate is a definitechemical'entity of. melting point one hundred and forty-six to onehundredandforty-seven degrees and having a chlorine content M67 .8percent and sulfur content of 5.09. percent. Because of its highmolecular weight (six hundred andeleventosix hundred and thirty-nine)and difiicult. combustibility, the number of hydrogenatoms in, themolecule is in doubt, and consequently its exact structure is uncertain.A solution of 62.8 parts by weight of this compound and 5.9 parts byweight of acetamide in one hundred and seventy-six parts by weight ofxylene is refluxed for six hours until evolution of SO had substantiallydwindled. The solution is concentrated and the resultant crystallineproduct removed by filtration and dried in air. An infrared spectrumshowed the compound to have an OH group, an NH group, an amide C=Ogroup, and a'methyl group.

Anzlysis.Calcd. for C10C110(OH) Cl, 64.5; N, 2.5. Found; Cl, 63.5; N,2.5.

Upon heating the product for twenty four hours at three hundred degreescentigrade with an excess of phosphorus pentachloride in -a sealed tube,and evaporating the reaction mixture under vacuum at one hundred degreescentigrade, the volatile substances are removed leaving a crystallinesubstance which upon recrystallization, melts at four hundred andeighty-five degrees centigrade, which is the melting point of theexpected and known derivative d-odecachloropentacyclo;(5;3.0.0. .0 .0decane, and has the correct percentage of chlorine for C Cl Example 2.Pr-epar ation of C C1 (OH) (NHCHO) NH CHO hydrate One part by weight ofthe intermediate chlorosulfonation product of Example 1 melting at onehundred and forty-six to one hundred and forty-eight degrees centigradeis dissolved in ten parts by weight of formamide at one hundred degreescentigrade. After twenty-four hours at this temperature, the reactionmixture is cooled and poured into distilled waterpThecolorlesscrystalline product which precipitates out, is filtered ofi" and airdried. Infra-red analysis shows the presence of the desired OH, NH andvamide C=.O groups,- as well as an additional shoulder in the carbonylregion.

Analysis.Calcd. for

- CmCl (OH) (NHCHO) .NHCHQH O 01, 59.7; N, 4.7. Found: 01, 60.7; N, 4.5

Example 3.Prpdriztion of O1oClio(OH) (No 0 oij g'ncmomc om expect forthe desired product.

Found: N, 3.6; 01,- 48.6.

Example 4.-Preparati0n a) C Cl (OH) (NHCOC H In two hundred andsixty-four parts of Xylene, 12.1 parts by weight of benzamide is reactedwith 62.8 parts by weight of the crystalline C Cl /ClSO H product,melting at onehundred and forty-six to one hundred and forty-eightdegrees. After four hours, the S0 evolution dwindles. On partialevaporation of the xylene and cool- 7 ing, a colorless crystallineproduct is obtained whose infra-red spectrum showed OH, -NH and amideC=O groups as well as C=C double bond vibrations characteristic of anaromatic ring.

Analysis.Calcd. for C Cl (OH) (NHCOC H Cl, 58.0; N, 2.3. Found: Cl,57.9; N, 2.3.

It is found possible to titrate the product in acetone solution usingtetrabutylamrnonium hydroxide (0.1N) as the base. The end point occursat the point where one molar equivalent of the base is added, showingthat the C Cl (OH)N-HCOC H is a monobasic acid.

Example 5.Preparation f C CI (OH)NHCOC H A mixture of 62.2 parts ofoctadecylamide (ten percent molar excess), one hundred and twenty-fiveparts of the crystalline product of hexachlorocyclopentadiene andchlorosulfonic acid, and two hundred and twenty parts of dry xylene areheated at reflux for one day, until S0 evolution dwindled. The xylene isevaporated under wateraspirator vacuum and the waxy residuerecrystallized from heptane and a white waxy solid is obtained, meltingpoint seventy to seventy-five degrees.

Analysis.Calcd. for C H O NCl N, 1.8. Found: N, 1.9.

Example 6.--Prepalration of As above, using 61.8 parts of oleamide (tenpercent molar excess). The residue on evaporation of the xylene is aliquid andcannot be induced to crystallize. v

The infra-red spectrum confirmed that the product has the structure.

Example 7.Preparati0n of A mixture of 62.8 {parts of the crystallinereaction prodnet of C Cl and ClSOgH is heated with 13.5 parts ofacetanilide in one hundred and eighty parts of xylene at reflux for sixhours, until S0 evolution dwindles. Cooling to room temperature gives acrystalline precipitate, 30.5 parts by weight. Its infra-red spectrumshows the characteristic amide carbonyl band at six microns.

Analysis.-Calcd. for C Cl (OH)N(COCH )C H Cl, 56.7. Found: Cl, 57.9.

Example 8.'Preparation 0f C Cl (OH)NI-ICHO A mixture of 31.3 parts ofthe crystalline reaction product of C Cl and C1SO H in one hundred andseventysix parts of xylene, mother liquor from a previous preparation ofC Cl (OH)NHCHO, is refluxed for several hours, then while maintainingreflux, 9.0 parts of formamide is added and reflux continued for thirtyhours. The mixture is then cooled to twenty to thirty degrees, and theresulting "crystalline precipitate filtered off. The mother liquor isemployed for a repeat run. The crystalline precipitate melts at threehundred and thirty-six degrees.

Analysis.-Calcd. for C Cl (OH)NI-ICHO: N, 2.6. Found: N, 2.6.

Example 9.--Preparation 0 f CmCl1n(OH)NHCOC=CHCH=CHO A mixture of 62.8parts of the crystalline product of C Cl and ClSO H and 26.8 parts offuramide in one hundred and seventy-six parts of xylene are refluxed forone day at the end of which time S0 evolution is negligible. On cooling,a dark amorphous precipitate is formed which is filtered and dried. Theinfra-red spectrum supports the structure, although some complexed orentrained furamide appeared to be present. The product is used in thecrude form.

Analysis.-Calcd. for

N, 3.7. Found: N, 4.2.

Example 10.--Preparati0n of (3 ,01 onn u ration-x3 11 A mixture of 62.8parts of the crystalline product of C Cl and ClSO I-I in one hundred andseventy-six parts of xylene is refluxed for one day with 13.5 parts ofaphenylacetarnide. On cooling, a precipitate is obtained which, byinfra-red, is established to have the desired C Cl (OH)NHCOCH C Hstructure.

Ana lySis.Calcd. for C Cl (OH)NHCOCH C H N, 2.2. Found: N, 2.5.

Exdmpie I 1 '.Preparation of C Cl (OH)-s'ubstituted polyamide Thirty-oneparts of the crystalline product of C Cl and chlorosulfonic acid ispulverized with thirty parts of a commercial polyamide derived fromethylenediamine and a fatty dibasic acid C H (COOH) and the mixture isheated at one hundred and forty to one hundred and fifty degrees foreighteen hours, at which time no further $0 was evolved. The product iscooled and the resulting resin is pulverized. The infra-redspectrumestablishes the presence of the C Cl (OH)N-RCOR' structure.

Example 12.--Prep*arati0'nof other representative compounds of thisinvention The chlorosulfonic acid intermediate ofhe'xachlorocyclopentadi'ene melting at one hundred and forty-six to onehundred and forty-eight degrees Centigrade is reacted with theappropriate amide as disclosed in the preceding examples. The followingcompounds are prepared (left hand column), in crude form. The right handcolumn gives the amides used.

I HO

1 1 Example 13.Formulatian of marine paint having antifowling propertiesThe following ingredients are blended and ground together in a ballmill.

Pounds per 100 gallons Ingredient:

Gum rosin, grade WW 277 Blown fish oil 118 Zinc stearate 18 Versamidepolyamide adduct of Example 11 197 1 Volume adjusted to 100 gal. byaddition of naphtha.

Example 14.Formulation of marine paint having antifouling properties Thefollowing ingredients are blended andground together in a ball mill.

Ingredient: Pounds per 100 gallons Rosin 311 Hydrogenated methylabietate 115.5 Coal tar naphtha 92.4

Mineral spirits (paint thinner) approx. 103.7

Di-atomaceous silica 103.7 C1OC11G(OH)NHCOCGH5 311 Lampblack l .0

The following ingredients are blended together in the indicatedproportions, in a ball mill.

Ingredient: Pounds per 100 gallons Rosin 265 Coal tar 80 Talc 80 Pineoil 42 C Cl (OH) (NHCOCH from Example 1. 200 High flash naphtha 135Mineral spirits, make up to volume.

1 2 Example 17.Another formulation of marine paint having anti foulingproperties The followin g ingredients are blended together in thedenoted proportions, in a roller mill.

Ingredient: Percent by weight Chlorinated rubber (Parlon S-125) 2.5Rosin 20.00 Dibutyl phthalate 0.30 Titanium dioxide pigment 21.65 Zincoxide 8.55 Cobalt naphthenate 0.05 Lead naphthenate 0.19Phenoxypropylene oxide 0.13 C C1 (OH)NCOC H -from Example 5 5.00 XyleneRemainder Example 18.Testing of paint formulations of the precedingexamples for antifouling properties The formulations disclosed in thepreceding examples are painted on steel test panels, allowed to dry andim- Inersed in sea Water at a sub-tropical location. At the same timeother identical panels are painted with control test formulationsidentical with these paint preparations except that theN-decachlorohydroxypentacyclodecylamide derivatives are omitted from theformulationThese test panels are immersed in the same sub-tropical seawater. After one month both the control test panels and the panelscontaining the active component are examined and compared. It is foundthat the control panels are heavily crusted with a mixed population ofbarnacles and other marine organisms, while the panels containing theactive anti-marine fouling component were not adversely affected.

Example 19.Testing of anti-marine fouling properties of differentproducts of this invention To eliminate variables due to the otheringredients in the paint formulations a simplified comparison test iscarried out by treating porous test panels with a number of the productsof this invention applied as a three percent solution of methyl isobutylketone. The panels are allowed to dry and are then immersed in sea Waterat a subtropical location where untreated test panels became heavilyfouled during the test interval. After a one month period the degree offouling control was observed according to the amounts of foulingorganisms found on the treated panel surface compared to identicaluntreated panels. The results are recorded on Table I below.

TABLE LPEROENT CONTROL OF FOULING BY INDICATED ORGANISMS Compound AlgaeAmphl- Annelida Barnacles Bryozoa Hydroids Mollusks Tunicates Micropodsfouling C1oCI1o(OH) (NHCHO) 100 100 100 100 100 100 100 100 100C1oOlm(OH)(NHC 00113) 100 100 100 95 100 100 100 100 100C1nC11o(OH)(NHCOCsH5) 100 100 100 100 100 100 100 100 100 CmClm(OH) (NHCOCHzCoHs) 100 100 100 100 100 100 100 CmCho(0H) (NHCONHz) 0 0 20 0 0 50100 50 0 C Ol (OH)- N 100 100 100 100 100 100 100 C O CmC11n(OH) NHC 0%O 13 14 What is claimed is: 6. A compound according to claim 2 of theformula C Cl (OH)NHCOCH C H E1 7. A compound according to claim 2 of theformula Cl R Q OlMOID-NH-COQ i ii o1 I -R' $11 0 1 r 01 o C V 9. Acompound according to claim 2 of thejormula wherein R is selected fromthe group consisting of hydrogen, lower alkyl, and phenyl; and R isselected from OwCIMOH) NHGOO the group consisting of phenyl,hydroxyphenyl, benzyl and phenoxy, and, when R is phenyl, R is loweralkyl; and X 20 is selected from the group consisting of oxygen andsulfur.

2. A compound according to claim 1 wherein X is CmClro(OH)-N oxygen.

3. A compound according to claim 2 wherein R is hydrogen and R isselected from the group consisting of 25 phenyl, phenoxy, hydroxyphenyland benzyl. References (med 4. A compound according to claim 2 of theformula Ungnade et al.: Chem. Rev., vol. 58 (1958), pages C C1 (OH)(NHCOC H 5. A compound according to claim 2 of the formula 30 LORRAINEA. WEINBERGER, Primary Examiner.

C Cl (OH)N(COCH )C H RICHARD K. JACKSON, Examiner 10. A compoundaccording to claim 2 of the formula

